DE102009020544A1 - Preparing a copolymer, useful to produce e.g. plastics, comprises providing a cyclodextrin compound, providing a metallocene compound with double bonds and providing a styrene compound, adding an initiator and polymerizing components - Google Patents

Abstract

Preparing a copolymer comprises (a) providing a cyclodextrin compound, (b) providing a metallocene compound with one or more polymerizable double bonds and providing a styrene compound, (c) adding an initiator, and (d) polymerizing the components from the step (b). Independent claims are included for: (1) the copolymer, obtained by the above method; (2) a composition comprising the copolymer and one or more smoke reducer comprising heavy metal compounds, cyanides and complex ferrocyanides, metal oxides, nickel-II-oxide, iron-III oxide, molybdenum VI oxide, vanadium V oxide, copper hydroxide phosphate, zinc borate, ammonium octamolybdate, aluminum hydroxide, magnesium hydroxide, ferrocene, iron acetonyl acetonate or iron-, manganese- or chromium-metal salts of 8-hydroxyquinoline; and (3) a fire protection composition comprising the copolymer and one or more flame retardant additives comprising hexabromocyclododecane, organic halo compounds, decabromodiphenyl ether, tetrabromobisphenol, inorganic halogen compounds, ammonium bromide, nitrogen compounds, melamine, melamine formaldehyde resin, inorganic hydroxide compound, magnesium-aluminum hydroxide, inorganic compounds, aluminum oxide, titanium dioxides, antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate, barium metaborate, tin oxide, siloxane compounds or phosphorus compounds.

Description

The The invention relates to a process for the preparation of improved burned Polymers of high-boiling plastics, in particular of polystyrene products. The invention further relates to improved combustion low-carbon polymers, the moldable plastics and their applications as moldings, packaging, a Insulating material, a foam or an expanded or extruded polystyrene rigid foam.

at the combustion of plastics (eg in waste incineration plants) arise large amounts of soot, consuming from the combustion exhaust gases must be filtered so that these do not enter the environment and cause damage there can.

Of the Soot produced during combustion is currently being used after the Combustion by means of suitable particle filters from the combustion exhaust gases deposited. The necessary filtering is technically complicated and causes high costs. The filtered soot particles must be disposed of separately, resulting in further costs.

Consequently There is an increased demand for polymers that are too low in size or soot-free plastics can be processed, because that could be the problem of environmental damage solved by soot particles right from the beginning be without extensive filtering in incinerators to drag.

ferrocene and its derivatives are used as Rußminderer in fire retardants used. Known smoke reducers are also heavy metal compounds, in particular cyanides and complexes ferrocyanides, metal oxides such as Nickel II oxide, ferric oxide, molybdenum VI oxide, vanadium V oxide as well as Copper hydroxide phosphate, zinc borate, ammonium octamolybdate, Aluminum hydroxide and magnesium hydroxide, with ferrocene being the most effective Means is.

Numerous patents have been published on the combustion processes of ferrocene, e.g. B. in diesel fuels ( US 4,389,220 ).

Out DE 10 2005 032 119 It is known that ferrocene and its derivatives are used as an additive for fuel improvement in fuel oil.

Also in the document DE 41 29 408 C1 Ferrocenes are used as fuel additives to reduce soot. Therein a device is described, with which the required amount of ferrocene can be fed via a grinder as a solid fuel.

As a carbon black reducer, free ferrocene is also known as an additive for polymers. So will in US 4,877,078 the addition of free ferrocene to polystyrene is described. From this polymer molded products can be produced.

Smoke-reduced polymer products, in particular polyvinyl chlorides are disclosed in US Pat. No. 3,935,142 described. PVC compositions have inherent self-quenching properties due to the high chlorine content. Nevertheless, it is precisely these bad burning properties that lead to the emission of large volumes of smoke when burning. The combustion products therefore contain the smallest carbon particles and partially burned polymer fragments. Accordingly, iron trimellitate salts are added to the PVC in order to reduce the smoke development on combustion.

A similar problem will be in US 4,049,618 described. There, free ferrocene compounds are added to the polymer to achieve improved smoke-evolving properties.

Also known is the incorporation of ferrocene and its derivatives into polycarbonates, polyesters ( DE 3 911 558 ) and polyurethane ( EP 0 414 868 ), or the addition of these as starting material during the preparation of the polymers.

Indeed is the addition of free ferrocene to polymers problematic, because ferrocene at temperatures above 100 ° C evaporated (vapor pressure 2.6 mbar at 100 ° C). Therefore, just now when burning the polymer, the effectiveness of the ferrocene not fully exhausted as a smoke reducer.

In addition, some stabilizers, such as barium-cadmium-zinc-phosphite systems are not compatible with free ferrocene and suppress the smoke reducing effect.

Therefore There is an increased demand for smoke-reduced polymers or compositions which burn soot-free.

Furthermore, the synthesis of some ferrocenyl-substituted styrenes in US Pat. No. 6,800,776 B1 proposed.

In the published patent application DE 3 419 788 A1 For example, copolymers are disclosed as electrical conductors or semiconductors in solar cells, as battery electrodes, or as materials for electrochemical membranes. Among others, the introduction of a substituted ferrocene molecule via polymerizable groups into the side chains of polymers such as polystyrene, polyvinyl chloride, polybutadiene, polyacrylate, etc. is mentioned. The incorporation into the main chain is effected by polycondensation or polyaddition in which the ferrocene is substituted with dicarboxylic acids or dicarboxylic acid esters or used as ferrocene diisocyanate. A main chain copolymerization of styrene and derivatized ferrocenes is not described.

In the patent US Pat. No. 6,458,907 B1 For example, polyvinyl diphenylferrocene is described and used as a negative resist for mask preparation in ion beam lithography. Copolymers of ferrocene derivatives with reactive unsaturated double bonds and further monomers, such as, in particular, acrylates or methacrylates, are known from this document. In US Pat. No. 6,458,907 B1 However, copolymers of derivatized ferrocene monomers and styrene monomers are also proposed.

The Flue gas density depends mainly on the soot, and this is very high in aromatic substances such as polystyrene, because most of the smoke contributes to the release of Aromatics used in condensed polyaromatic systems in direct soot precursors can be converted. Currently come for the polystyrene as a smoke reducer Eisenacetonylacetonat and heavy metal salts (Fe, Mn, Cr) of 8-hydroxyquinoline.

polystyrene burns flickering with a yellow, heavy sooting flame. After removing the ignition source, the plastic burns further.

The EPS (expanded polystyrene rigid foam) as well as the XPS (extruded polystyrene hard foam) burn strongly sooty. Brominated flame retardants such as HBCD (hexabromocyclododecane) are often added to insulating materials made of EPS. However, the requirement for reduced flammability and reduced fuming generally preclude one another, since well-scavenging polymers convert most of the carbon compounds to CO ₂ and therefore produce less particulate matter.

The It is an object of the present invention to provide polymer products in particular polymers of strong sooting plastics such To provide polystyrene, which release less soot when burned.

Farther It was an object of the present invention to provide a method develop with which such flame-improved polymers efficiently and can be produced inexpensively.

These Tasks are achieved by the method of claim 1 and the copolymer solved according to claim 9 to 12.

• a) Bereitstellen einer Cyclodextrinverbindung,
• b) Bereitstellen einer Metallocenverbindung mit einer oder mehreren polymerisierbaren Doppelbindungen und Bereitstellen einer Stryrolverbindung,
• c) Zugabe eines Initiators,
• d) Polymerisation der Komponenten aus b) zur Herstellung des Copolymers.

In particular, the above object is achieved by a process for producing a copolymer, comprising the steps:

• a) providing a cyclodextrin compound,
• b) providing a metallocene compound having one or more polymerizable double bonds and providing a styrene compound,
• c) addition of an initiator,
• d) polymerization of the components from b) for the preparation of the copolymer.

The Metallocene compound may hereby preferably be a titanocene compound, Cobaltocene or Manganocenverbindung be. Especially however, a ferrocene compound is preferred.

The Procedural steps can be in any order respectively. In particular, the steps may preferably a) and b) occur simultaneously or in a reversed order, ie b)> a) or a)> b). It is however, the method prefers to carry out in the order a)> b)> c)> d).

Surprised it has been found that styrene compounds with metallocene compounds, especially ferrocene compounds, and most preferably vinylferrocenes, utmost can be effectively copolymerized. The metallocene compounds consist of a Metallocengrundbaustein, in which at one or both cyclopentadienyl polymerizable (z. B. unsaturated alkenyl radicals) substituents.

Farther is used for the polymerization process according to the invention requires a cyclodextrin compound. The cyclodextrin allows the copolymerization of the two monomer species in a particularly advantageous and simple way. Without one Certain theory is believed to be determined by the cyclodextrin the polymerizable monomers used (styrene compounds and metallocene compounds) also in aqueous solvent systems become soluble. Organic solvents are thus no prerequisite for the course of the reaction. However, the person skilled in the art is not interested in any particular solvent system bound and can choose these freely, that the Copolyermisationsreaktion invention expires.

The Starting monomers themselves are complexed with cyclodextrin in the aqueous solvent systems of the invention soluble and thus accessible to polymerization. It is also particularly advantageous that the copolymer product produced from the solution fails, since only the metallocene units in the copolymer are complexed with cyclodextrin, while the polystyrene decomplexes with increasing chain length becomes.

This is confirmed experimentally by the measured 2D ROESY NMR spectrum on a poly (styrene-co-vinylferrocene). The protons of the cyclopentadienyl rings of the vinylferrocene interact with those of the cyclodextrin - whereas the styrene units are decomplexed.

The Polymerization reaction can be cationic, anionic, under the conditions the Ziegler-Natta polymerization or radical, wherein radical reactions are preferred. In cationic polymerization The styrene monomers must be in high excess present to be incorporated significantly in the main chain.

The Allow copolymers according to the present invention Therefore, preferably by free radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization produce. All suitable radical starters can be used become; the skilled person is not here to a specific initiator bound. However, particularly preferred is the compound 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044) used as initiator.

In In a preferred embodiment, the method of Invention under argon atmosphere carried out.

The Copolymers may preferably have molecular weights (determined by MALDI-TOF) between 5,000 and 25,000 g / mol, preferably 10 000 g / mol.

In A development of the inventive method comprises the method a subsequent step after step e), wherein the unbound free Cyclodextrin is removed from the polymer produced. This can for example, by washing with additional solvent, u. a. done with water.

Preferred cyclodextrins for the process are:
Alpha, beta or gamma cyclodextrins or derivatives such as CD-CAVASOL ^® or CAVAMAX ^®.

Especially preferred are beta-cyclodextrins, including in particular: HPBCD (hydroxypropyl-beta-CD), HEBCD (hydroxyethyl-beta-CD), DIMEB (heptakis (2,6-dimethyl) -beta-CD), TRIMEB (heptakis (2,3,6-trimethyl) -beta-CD), EPC (CD crosslinked with Epichlorohydrin), HP-beta-CD, HE-beta-CD, per-Ac-beta-CD.

Especially The process is advantageous if in step a) methylated beta-cyclodextrin is submitted. Even more preferred, however, are methylated cyclodextrins like TRIMEB, DIMEB, RAMEB.

At the preferred is the randomly methylated RAMEB (randomly methylated beta-CD).

Farther preferred is the use of an aqueous solvent system in the method according to the invention.

Under an aqueous solvent system in the sense of Invention is to be understood as a solvent which is used for largest part consists of water. Preferably comprises this system contains more than 60.0% by weight of water, more preferably more as 80.0 wt .-% water, and most preferably a system with more than 95.0% by weight of water. Systems apart from impurities (which can make up a maximum of 0.5% by weight) from 100 Wt .-% water, are also particularly preferred. It is also conceivable that the solvent system in addition to the Water content still includes other organic solvents. Preference is given to the water content of these solvent systems from 10.0 to 95.0% by weight of water. Particularly preferred are 50.0 to 90.0% by weight of water. The person skilled in the art will be aware of the aqueous solvent system and if present, the organic solvent components adjust so that in particular the cyclodextrin compound as also the metallocene compound and the styrene compound is sufficient Have solubility to complete the polymerization reaction allow. The cyclodextrin compound becomes the solubility the metallocene compound and the styrene compound in the aqueous System increased. This will make one on the environmentally sound Solvent water based, effective and cost effective Copolymerization of metallocene compound with the styrene compound allows. In particular, with the inventive Process no organic solvents for the polymerization is needed. By the invention Process, it is now possible styrene compounds and metallocene compounds to polymerize in an aqueous solvent system. Particularly elegant is that the polymerized product by itself precipitates out of solution and thus easily recovered can be, since with increasing degree of polymerization, the polystyrene is decomplexed.

Prefers The metallocene and the styrene compound is in a ratio from 1: 1 to 1: 200 mol .-% submitted. Even more preferred is a ratio from 1:10 to 1: 100 mol%, most preferably 1:20 to 1:80 mol%.

In In a further development of the invention, the metallocene compound based on the total amount of styrene compound and metallocene compound in a ratio greater than or equal to 1.1 mol .-% initially charged, preferably in a ratio greater or equal to 1.8 mol .-%, particularly preferably larger or equal to 3.0 mol%, most preferably from 2.0 to 20.0 mol%.

It it is preferred that the cyclodextrin compound based on the total amount to styrene compound and metallocene compound in a ratio greater than or equal to 25 mol .-% is submitted. Yet more preferably, the template is larger in proportion or equal to 30 mol .-%, more preferably greater or equal to 45 mole%, more preferably in the range of 35 to 95 mol%, most preferably in the range of 40 to 75 mol%, most preferably in the range of 45 to 55 mole%.

In experimental series, the amounts of metallocene (here vinylferrocene) and cyclodextrin were reduced in order to determine their quantitative influence on the formation of soot. The results of these investigations are shown in the following Table 1. example Proportion of vinylferrocene (based on the total amount of monomers) Proportion of cyclodextrin (based on the total amount of styrene compound and ferrocene compound) soot formation 1 2 mol% 50 mol% no soot formation 2 2 mol% Polymerization in bulk without cyclodextrin weak soot to the end of the burn Comparative Examples V3 1.0 mol% 50 mol% still soot formation V4 0.5 mol% 50 mol% still soot formation V5 0.25 mol% 50 mol% still soot formation V6 2 mol% 20 mol% still soot formation Table 1

The Experiments with 0.25, 0.5 and 1.0 mol% vinylferrocene were possible do not completely reduce soot formation. However, at a content of the vinylferrocene of 2 mol%, it was no soot formation in connection with a high proportion of cyclodextrin more.

Also the product of 2 mole% vinylferrocene and 20 mole% cyclodextrin (based on the monomers styrene and 1: 1 vinylferrocene) was tested to check the extent to which the cyclodextrin a Role in the combustion plays. The 20 mol .-% cyclodextrin relate on the amount of styrene plus the amount of substance to complete Complexing the vinylferrocene. That is, the amount of Cyclodextrin is 20 mol% of the styrene amount (eg 21.90 mmol) plus the same amount of cyclodextrin as on submitted vinylferrocene (eg 0.44 mmol), ie a total of z. B. 4.82 mmol cyclodextrin. Since this polymer still burns on burning, the cyclodextrin support the burning improvement. To the complete Soot avoidance becomes a certain minimum quantity Cyclodextrin needed.

In Further experiments investigated whether free ferrocene and / or free cyclodextrin in combination with a polystyrene to similar Results as in the copolymers of the present invention Invention.

The Stir free cyclodextrin into a styrene compound is not enough, to a soot-free combustion cause. The invention thus sets a metallocene component ahead.

Also Examinations with free ferrocene (2 mol .-%) showed that the Soot formation neither by stirring in substance still in combination with cyclodextrin in aqueous solution can be reduced.

The mere mixing of the components does not result to the desired success.

Indeed it was found that the copolymerization of vinylferrocene with styrene in substance improves the burning properties, as the Only weakly smoke the polymer until the end of the combustion. For example, the compound has polystyrene-co-polyvinylferrocene in itself a certain soot-reducing effect.

Around completely curb soot formation but not only the polymerisation of a metallocene compound with a styrenic compound, it also needs a bond (presumably a complex formation) between the metallocene units in the copolymer and the cyclodextrin compound.

in principle can all known styrene compounds and metallocene compounds as monomers in the process according to the invention be used.

Preferably, the styrenic compounds in the process of the invention comprise one or more of the following list:
Styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene, p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesul fonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene, 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene.

Especially preferred are styrene or alpha-methylstyrene.

When Metallocene compounds can be any suitable metallocenes employed in the process according to the invention provided they have one polymerizable group. Therefore, metallocenes are particularly suitable with unsaturated functional groups. Vinyl groups are particularly suitable.

Furthermore, the metallocene compound having one or more polymerizable double bonds in the process according to the invention preferably comprises one or more from the following list:
a ferrocene compound, a titanocene compound, cobaltocene compound, a manganocene compound,
Vinylferrocene, divinylferrocene, ferrocenylsilane, ferrocenyltrimethylsilane, isopropenylferrocene, ferrocenylethylmethacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate, 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenylethylacrylate, ferrocenylmethacrylate, p-ferrocenylstyrene, ethynylferrocene, ferrocenylmethylacrylamide.

Divinylferrocene or multifunctionalized ferrocenes may be especially are preferably used.

Often, but not necessarily, the process of the invention includes the provision and use of one or more other comonomers in the polymerization reaction, which are preferably selected from the following list:
Esters of acrylic acid or methacrylic acid of alcohols having up to 8 carbon atoms, methyl methacrylate, n-butyl acrylate, t-butyl acrylate,
N-vinyl compounds, vinyl carbazole,
unsaturated carboxylic acids, maleic anhydride, N-phenylmaleimide,
Methylstyrene, nuclear halogenated styrene compounds, nuclear alkylated styrene compounds,
Compounds containing two polymerizable double bonds, butadiene, divinylbenzene or butadiene diacrylate.

This The above presented inventive reaction process is in the state of Technique unknown. Especially new is the copolymerization the metallocene with the styrene compound and thus the preparation a chemical compound between styrene and metallocenes in the Plastic in an aqueous solvent system.

In order to The production of the copolymer is extremely simplified and environmentally friendly made, because it can do without organic solvents are needed and the discharge of the polymer product no further cleaning steps besides the optional washing.

In addition to the process, the above-described objects are also achieved by a copolymer preparable by the process according to the invention or alternatively by a copolymer comprising monomer units of a styrene compound and monomer units of a metallocene compound, wherein the metallocene units of the copolymer comprise one or more of the following monomer units:
a ferrocene compound, a titanocene compound, cobaltocene compound, a manganocene compound,
Vinylferrocene, divinylferrocene, ferrocenylsilanes, ferrocenyltrimethylsilane, isopropenylferrocene, ferrocenylethylmethacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate, 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenylethylacrylate, ferrocenylmethacrylate, p-ferrocenyl-styrene, ethynylferrocene, ferrocenylmethylacrylamide,
and the styrenic compound comprises one or more of the following monomer units:
Styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene, p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesulfonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene , 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene.

In principle, the copolymer of the present invention may consist of any suitable polymerizable metallocene derivative. These derivatives consist of a metallocene building block having substituents on one or both of the cyclopentadienyl rings which allow copolymerization with the reactive double bonds of the styrene compounds. Particularly preferred are polystyrene-co-polyvinylferrocene copolymers, wherein the styrene units of the copolymer one or more of following monomer units include:
Styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene, p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesulfonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene , 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene.

Likewise, the skilled person is not limited in the choice of the styrene compound, as long as it can be copolymerized with a polymerizable metallocene derivative. A further preferred embodiment therefore comprises a polystyrene copolymer comprising monomer units of styrene and monomer units of a metallocene compound, the metallocene units of the copolymer comprising one or more of the following monomer units:
a ferrocene compound, a titanocene compound, cobaltocene compound, a manganocene compound,
Vinylferrocene, divinylferrocene, ferrocenylsilanes, ferrocenyltrimethylsilane, isopropenylferrocene, ferrocenylethylmethacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate, 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenylethylacrylate, ferrocenylmethacrylate, p-ferrocenylstyrene, ethynylferrocene and ferrocenylmethylacrylamide.

Surprisingly, it has been found that such copolymers have improved burning properties. Incomplete combustion produces not only carbon dioxide but also carbon monoxide (CO) and carbon black (C). The copolymer of the present invention, however, allows better combustion to CO ₂ without incompletely burned polymer particles as smoke.

This is based on the comparison images in 1 clearly visible. On the left side, a polystyrene-vinylferrocene copolymer (PS-co-PVFc) according to the present invention has been burned. On the right side, a conventional polystyrene without ferrocene comonomers after combustion is shown. In comparison, one recognizes the enormous reduction by the copolymerization with vinylferrocene.

The Metallocene units in the copolymer could be over the catalytic effect of the metal in the metallocene core to a more complete implementation of the carbon-containing polymer components and a low-carbon combustion to carbon dioxide to lead.

Of the Incorporation in the polymer backbone could increase the volatility of the metallocene (eg ferrocene) at higher temperatures bypass and thus a higher effectiveness of the catalytic Ensuring metal core (eg iron) during combustion.

Even though the polystyrene-co-polyvinylferrocene polymers listed above have a lower smoke, takes their Combustion not completely free of soot, because the At the end of the combustion there is a slight development of soot. An even higher fuel improvement is surprisingly achieved in that the metallocene groups in the copolymer together with cyclodextrin present.

Thereby a completely soot-free combustion is guaranteed.

A particularly preferred embodiment of the invention therefore a copolymer of the present invention, further comprising Cyclodextrin.

Without limited to the specific binding of cyclodextrin it is believed that the cyclodextrin with the metallocene group in the copolymer enters into a complex-like bond. Preferably, this includes Complex according to the invention therefore complexed Cyclodextrin. Therein, the cyclodextrin is preferably with the metallocene group connected to the copolymer via a complex bond. Especially between 30 and 99% of all metallocene units are preferred complexed to a cyclodextrin. More preferred are between 50 and complexing 85% of all metallocene units with a cyclodextrin, most preferably more than 55%. Preferably, between 1 and 20% of all styrene units in the copolymer complexed with a cyclodextrin, preferably less than 5%. The complex binding occurs without the invention to want to commit to a particular theory, through interaction between the metallocene and binding sites on the inside of the Cyclodextrin.

Next the metallocene group and the styrene group can still additional comonomers are incorporated into the polymer backbone. The resulting copolymer can in particular further vinyl group-containing Contain monomers.

alternative Polymer blends can be used as polymer blends by the subsequent Mixing of other polymers can be achieved.

Therefore The present invention also deals with a polymer blend comprising one or more of the invention Copolymers comprising one or more further admixed Polymer components.

These Mixtures advantageously have a styrene content of at least 50 wt .-% of styrene compound.

Other vinyl group-containing monomers may preferably be used, for example unsaturated nitriles, such as acrylonitrile, methacrylonitrile,
Methylstyrene, ring-halogenated or ring-alkylated styrenes,
Esters of acrylic acid or methacrylic acid of alcohols having up to 8 carbon atoms, such as. B. preferably methyl methacrylate, n-butyl acrylate, t-butyl acrylate,
N-vinyl compounds, such as vinyl carbazole,
or also compounds which contain two polymerisable double bonds, such as butadiene, divinylbenzene or butadiene diacrylate,
or unsaturated carboxylic acids such as maleic anhydride or N-phenyl-maleimide.

The smoke reducing properties in a composition comprising the copolymer according to the invention can be further improved, furthermore comprising one or more smoke reducers from the following list:
Heavy metal compounds, cyanides and complexes ferrocyanides, metal oxides, nickel II oxide, iron III oxide, molybdenum VI oxide, vanadium V oxide, copper hydroxide phosphate, zinc borate, ammonium octamolybdate, aluminum hydroxide, magnesium hydroxide, ferrocene, iron acetonyl acetonate and Fe-, Mn or Cr metal salts of 8-hydroxyquinoline.

The Copolymers of the invention or polymer blends may also contain conventional additives, such as anti-dripping agents, very finely divided inorganic compounds, lubricants and mold release agents, Nucleating agents, antistatic agents, stabilizers, fillers and reinforcing agents as well as dyes and pigments.

Called in particular, hexabromocyclododecane, chlorinated paraffin, as well as synergists for flame retardants, such as dicumyl and highly decomposable organic peroxides; also antistatic agents, stabilizers, Dyes, lubricants, fillers and foaming Antiverklebend acting substances, such as zinc stearate, Melaminformaldhydkondensate or silica, as well as means for shortening the Entformzeit during foaming, such as glycerol esters or Hydroxycarboxylic.

The Additives may vary depending on the intended effect homogeneously distributed in the particles or as a surface coating available.

The usable inorganic compounds include compounds of a or more metals of the 1st to 5th main group and the 1st to 8th Subgroup of the Periodic Table, preferably the 2nd to 5th main group and the 4th to 8th subgroup, particularly preferably the 3rd to 5th Main group and the 4th to 8th subgroup with the elements oxygen, Sulfur, boron, phosphorus, carbon, nitrogen, hydrogen and / or Silicon.

Examples of such compounds are oxides, hydroxides, hydrous oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates. These include, for example, TiN, TiO ₂ , SnO ₂ , WC, ZnO, Al ₂ O ₃ , ZrO ₂ , Sb ₂ O ₃ , SiO ₂ , iron oxides, NaSO ₄ , BaSO ₄ , vanadium oxides, zinc borate, silicates such as Al silicates, Mg Silicates, one, two, three-dimensional silicates, mixtures and doped compounds are also useful. Furthermore, these nanoscale particles can be surface-modified with organic molecules to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be produced.

The average particle diameter is less than or equal to 200 nm, preferably less than or equal to 150 nm, particularly preferably 1 to 100 nm.

Particle size and particle diameter always means the average particle diameter d50, he mediated by ultracentrifuge measurements W. Scholtan et al., Colloid-Z. and Z. Polymere 250 (1972), pp. 782 to 796 ,

When Fillers and reinforcing materials come z. B. Glass fibers, optionally cut or ground, glass beads, Glass spheres, a platelet-shaped reinforcing material, such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, Wollastonite, Mika, carbon fibers or their mixture into consideration. Preferably, cut as a reinforcing material or ground glass fibers used.

preferred Fillers that can also have a reinforcing effect are glass beads, mica, silicates, quartz, talc, titanium dioxide or Wollastonite.

By Copolymerization of styrene compounds with metallocene-containing monomers, especially in their complexation with cyclodextrins, is surprising a strong soot development during the combustion of the polymer products prevented.

in principle However, close the demand for reduced flammability and reduced smoke. To make a substance flame retardant (reduced flammability), the oxygen supply should be be stopped while looking for a soot-free Combustion should ensure a good supply of oxygen.

Therefore the present copolymers are not superficially suitable necessarily as a fire retardant. Nevertheless, the strong smoke is in fires a not to be underestimated disadvantage, which reduces the life expectancy of trapped persons.

Therefore could the advantageous properties regarding Smoke development of the present copolymers also in fire protection compositions be beneficial.

insulation materials Often, bromine-containing flame retardants such as HBCD (hexabromocyclododecane) added.

A refinement according to the invention is therefore furthermore a copolymer according to the invention, polymer blends or a fire protection composition, preferably also comprising one or more flameproofing additives from the following list:
Hexabromocyclododecane, organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine-formaldehyde resins, inorganic hydroxide compounds such as Mg-alhydroxide, inorganic compounds such as aluminum oxides, titanium dioxides, antimony oxides, barium meta-borate, hydroxoantimonate, zirconium oxide, zirconium hydroxide , Molybdenum oxide, ammonium molybdate, tin borate, ammonium borate, barium metaborate and tin oxide, and siloxane compounds.

As flame retardant compounds can also phosphorus compounds, as described in the EP 363 608 A . EP 345 522 A or EP 640 655 A are described used.

These Fabrics are with preference in proportions of 0.01 to 20% by weight, based on the total molding composition, in the inventive Polymer composition included.

In This combination could therefore be a flame retardant but still provided smoke reduced polystyrene replacement become.

preferred These compositions are used in insulating materials, in particular of EPS.

The invention prevents soot formation during the combustion of plastics. However, the copolymers or compositions of the invention have still further advantages. In addition to cost savings in the purification of industrial waste gases and those from waste incineration plants, the pollution of the environment can be reduced by reducing the development of soot in uncontrolled or improper burns of plastics. Thus, the environmental impact of waste incineration plants that fall outside the scope of European air quality directives is also reduced. The incorporation of the metallocene in aqueous solution has a cost advantage over other similar processes that work with organic solvents, as well as simplification in the handling and disposal of waste / by-products generated during production. Those caused by the necessary production change Costs are kept to a minimum by the low amount of metallocene required and the simple manufacturing process. Thus, the cost and environmental footprint of the production, use and disposal of plastics can be significantly improved.

After all Therefore, the present invention also includes the uses of products according to the invention for the preparation of a Plastic, a fire protection composition or fire retardant, a Shaped body, a packaging of an insulating material, a foam or an expanded or extruded polystyrene hard foam.

use find the inventive copolymers also as a molding composition Production of a molded product or molded article with the above-described advantageous properties.

The Polymer blends of the present invention can be used for Production of moldings of any kind can be used. In particular, moldings can be injection molded getting produced. Examples of producible moldings are: housing parts of any kind, eg. For household appliances, like juicers, coffee makers, blenders, office machines, Computers, printers, monitors or cover plates for the Construction sector and parts for the motor vehicle sector.

plastics, which are based on styrene and styrene-containing copolymers are produced in large quantities and in many areas of the Technique used. Of great importance here also foamed products.

The EPS (expanded polystyrene rigid foam) as well as the XPS (extruded Polystyrene foam) burn strong sooty. Therefore are the present copolymers just as substitutes for Foam products and especially EPS or XPS of interest.

application finds the present inventive low carbon polystyrene copolymer especially in hard foams.

The Production of foams from the starting polymers can Here, as usual, directly by gassing of the polymer in the extruder and subsequent foaming Plates or by extrusion to minigranulat, containing propellant impregnated and foamed, take place.

For the production of foams are the expandable Styrolpolymerisatperlen in a known manner by heating to temperatures above its Softening point, for example with hot air or preferably expanded with steam. The resulting foam particles can after cooling and optionally an intermediate storage be further foamed by reheating. Finally they can in a known manner in non-gastight closing Molds are welded to form parts.

Further information on the customary impregnation, extrusion and foaming processes can be found, for example, in US Pat Kunststoffhandbuch, volume 5, polystyrene, edited by R. Vieweg and G. Daumiller, Carl-Hanser-Verlag Munich, 1969 ,

The polymer products according to the invention are preferably used as substitutes for polystyrenes in foamed or unfoamed form, eg. As in assembly materials, in mattresses, especially latex mattresses, in the back coatings of carpets, in rubber products, in Styropor ^® , in mounting foams, thermal insulation and in adhesives, rubber, also in Kunstlatexprodukte, in plastic housings of electrical appliances, in refrigerators, in disposable tableware, Packaging and sales trays.

After all The object of the present invention is the use of one of products according to the invention in the vehicle industry, construction, electrical or office equipment or in packaging or in the advertising sector.

in the The invention will become more apparent from the following example explained.

Example 1: Preparation of an Inventive Polystyrene-co-Polyvinylferrocens

Very good results can be achieved with the following experimental procedure: A 40% strength by weight solution of RAMEB (3) in dist. Water (29.28 g, 22.35 mmol) is present in a 100 mL flask and purged with argon for 5 min.

First Vinylferrocene (2) (94.78 mg, 0.45 mmol) is dissolved at 50 ° C and then styrene (1) (2.5 mL, 21.90 mmol) was added.

Of the Initiator VA-044 (4) (72.27 mg, 0.22 mmol) is placed in a Schlenk flask weighed, in 1.0 mL dist. Water under argon atmosphere dissolved and added to the reaction mixture by syringe.

Mol. Masse: (104,15)_m g·mol^–1 + (212,07 + 1310)_n g·mol^–1 Summenformel: (C₈H₈)_m(C₁₂H₁₂Fe)_n(RAMEB)_n Ausbeute: 3,2 g Tg: 107°C MALDI-TOF: m/z 1,0·10⁴ After a reaction time of 2 hours, the polystyrene-co-polyvinylferrocene (PS-co-PVFc) (5) precipitates as a yellow solid. The polymer is washed with dist. Washed water and dried.

Molar mass: (104.15) _m g · mol ^-1 + (212.07 + 1310) _n g · mol ^-1 Molecular formula: (C ₈ H ₈ ) _m (C ₁₂ H ₁₂ Fe) _n (RAMEB) _n Yield: 3.2 g Tg: 107 ° C MALDI-TOF: m / z 1.0 · 10 ⁴

Comparative Example 2:

Under the same conditions as in Example 1 above was the copolymerization of styrene and vinylferrocene with the addition of a smaller amount investigated on cyclodextrin. Here were only 20 mol .-% cyclodextrin used. The 20 mole% cyclodextrin refers to styrene plus the amount of substance to completely complex the Vinylferrocens. That is, the amount of cyclodextrin was 20 mole% of 21.90 mmol styrene plus 0.44 mmol for complexation of the vinylferrocene, thus a total of 4.82 mmol.

The Result of this investigation was that the connection with this lower cyclodextrin concentration still burned under combustion.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 4389220 [0006]
• - DE 102005032119 [0007]
• - DE 4129408 C1 [0008]
• - US 4877078 [0009]
• US 3935142 [0010]
• US 4049618 [0011]
• - DE 3911558 [0012]
• - EP 0414868 [0012]
• - US 6800776 B1 [0016]
• - DE 3419788 A1 [0017]
• - US 6458907 B1 [0018, 0018]
• - EP 363608 A [0096]
• EP 345522A [0096]
• - EP 640655 A [0096]

Cited non-patent literature

• W. Scholtan et al., Colloid-Z. and Z. Polymere 250 (1972), pp. 782 to 796 [0087]
• - Kunststoffhandbuch, volume 5, polystyrene, edited by R. Vieweg and G. Daumiller, Carl-Hanser-Verlag Munich, 1969 [0109]

Claims (18)

A process for producing a copolymer comprising the steps: a) providing a cyclodextrin compound, b) Providing a metallocene compound having one or more polymerizable double bonds and providing a styrene compound, c) Addition of an initiator, d) polymerization of the components from b) for the preparation of the copolymer. The method of claim 1, wherein in step a) methylated beta-cyclodextrin is submitted. Method according to one of claims 1 or 2 comprising as solvent a aqueous solvent system. Method according to one of claims 1 to 3, wherein the metallocene compound based on the total amount Stryne compound and metallocene compound in a ratio greater than or equal to 1.0 mol .-% is submitted. Method according to one of claims 1 to 4, wherein the cyclodextrin compound based on the total amount to styrene compound and metallocene compound in a ratio greater than or equal to 25 mol .-% is submitted. Method according to one of claims 1 to 5, wherein the styrenic compound is one or more of the following List includes: Styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene, p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesulfonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene, 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene. Method according to one of claims 1 to 6, wherein the metallocene compound with one or more polymerizable Double bonds one or more of the following list includes: a Ferrocene compound, a titanocene compound, cobaltocene compound a manganocene compound, Vinylferrocene, divinylferrocene, Ferrocenylsilane, ferrocenyltrimethylsilane, isopropenylferrocene, Ferrocenylethyl methacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate, 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenyl ethyl acrylate, Ferrocenyl methacrylate, p-ferrocenyl-styrene, ethynylferrocene, ferrocenylmethylacrylamide. Method according to one of claims 1 to 7, wherein one or more other comonomers in the polymerization reaction be used and selected from the list below become: Esters of acrylic acid or methacrylic acid of alcohols containing up to 8 carbon atoms, methyl methacrylate, n-butyl acrylate, t-butyl acrylate, N-vinyl compounds, vinyl carbazole, unsaturated Carboxylic acids, maleic anhydride, N-phenylmaleimide, Methyl styrene, nuclear halogenated styrene compounds, nuclear alkylated styrene compounds, links containing two polymerizable double bonds, butadiene, divinylbenzene or butadiene diacrylate. Copolymer producible by a method according to a of claims 1 to 8. A copolymer comprising monomer units of a styrenic compound and monomer units of a metallocene compound, wherein the metallocene units of the copolymer comprise one or more of the following monomer units: a ferrocene compound, a titanocene compound, a cobaltocene compound, a manganocene compound, vinylferrocene, divinylferrocene, ferrocenylsilanes, ferrocenyltrimethylsilane, isopropenylferrocene, ferrocenylethylmethacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate , 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenylethyl acrylate, ferrocenyl methacrylate, p-ferrocenyl-styrene, ethynylferrocene, ferrocenylmethylacrylamide, and the styrenic compound include one or more of the following monomer units: styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene , p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesul fonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene, 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene. Polystyrene-co-polyvinylferrocene copolymer, wherein the styrene units of the copolymer one or more of the following Monomer units include: Styrene, methylstyrene, halo-substituted or alkyl-nucleus-substituted styrene compounds, p-methylstyrene, p-chlorostyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-ethyloxycarbonyloxystyrene, 4-benzyloxystyrene, 4-methanesulfonyloxystyrene, alpha-methyl-4-acetoxystyrene, 4-tert-butoxycarbonyloxstyrene, 4-trichloroacetoxystyrene, t-butoxycarbonylstyrenes, styrenesulfonic acid and chloromethylstyrene. Polystyrene copolymer comprising monomer units of the styrene and monomer units of a metallocene compound, wherein the metallocene units of the copolymer one or more of the following Monomer units include: a ferrocene compound, a titanocene compound, Cobaltocene compound a manganocene compound, vinyl ferrocene, Divinylferrocene, ferrocenylsilanes, ferrocenyltrimethylsilane, isopropenylferrocene, Ferrocenylethyl methacrylate, p-ferrocenylphenylacetylene, ferrocenylmethylmethacrylate, 2-carboxymethyl-3-ferrocenyl-5-norbornene, ferrocenyl ethyl acrylate, Ferrocenyl methacrylate, p-ferrocenyl-styrene, ethynylferrocene and Ferrocenylmethylacrylamid. Copolymer according to one of claims 9 to 12, further comprising cyclodextrin. Composition comprising the copolymer according to one of claims 9 to 13, further comprising one or several smoke reducers from the following list: Heavy metal compounds, Cyanides and complexes ferrocyanides, metal oxides, nickel (II) oxide, Ferric oxide, molybdenum VI oxide, vanadium V oxide, copper hydroxide phosphate, Zinc borate, ammonium octamolybdate, aluminum hydroxide, magnesium hydroxide, Ferrocene, iron acetonylacetonate and Fe, Mn or Cr metal salts of 8-hydroxyquinoline. A fire retardant composition comprising the copolymer according to any of claims 9 to 13 or the composition according to claim 14, further comprising one or more flame retardant additives the following list: Hexabromocyclododecane, organic halogen compounds, Decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds, Ammonium bromide, nitrogen compounds, melamine, melamine-formaldehyde resins, inorganic hydroxide compounds, Mg-Alhydroxid, inorganic compounds, Aluminas, titanium dioxides, antimony oxides, barium metaborate, hydroxoantimonate, Zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, Tin borate, ammonium borate, barium metaborate, tin oxide, siloxane compounds and phosphorus compounds. Use of any of the products according to any one of the claims 9 to 15 for the production of a plastic, a fire protection composition or fire retardant, a molded article, a packaging, an insulating material, a foam or an expanded or extruded polystyrene rigid foam. Use of any of the products according to any one of the claims 9 to 15 in the vehicle industry, construction, electrical or office equipment or in the packaging or advertising sector. Shaped body comprising the copolymer according to one of claims 9-13.